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Metal-Exchanged Β Zeolites As Catalysts for the Conversion of Acetone to Hydrocarbons

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Metal-Exchanged Β Zeolites As Catalysts for the Conversion of Acetone to Hydrocarbons Materials 2012, 5, 121-134; doi:10.3390/ma5010121 OPEN ACCESS materials ISSN 1996-1944 www.mdpi.com/journal/materials Article Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons Aurora J. Cruz-Cabeza †, Dolores Esquivel, César Jiménez-Sanchidrián and Francisco J. Romero-Salguero * Departamento de Química Orgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica (IUIQFN), Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie, Ctra. Nnal. IV, km 396, Córdoba 14014, Spain; E-Mails: [email protected] (A.J.C.-C.); [email protected] (D.E.); [email protected] (C.J.-S.) † Present address: Van’t Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +34-957-212-065; Fax: +34-957-212-066. Received: 30 November 2011; in revised form: 22 December 2011 / Accepted: 24 December 2011 / Published: 5 January 2012 Abstract: Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Brönsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Brönsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion), the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite). We propose different reactions mechanisms in order to explain the final product distributions. Keywords: zeolite β; ion exchange; characterization; acidity; pyridine; acetonitrile; acetone conversion; hydrocarbons; isobutene; mesitylene Materials 2012, 5 122 1. Introduction As a result of increasing oil prices, the conversion of different low molecular weight organic molecules into gasoline has attracted much attention in recent years [1,2]. Among those precursors of gasoline, different C1-C4 oxygenates are good candidates. In particular, acetone constitutes a real alternative source of hydrocarbons since acetone is readily available as a secondary product in propylene oxide production and in phenol synthesis from cumene [3]. There is currently a critical need for the development of commodity chemicals, energy, and materials from renewable biobased feedstocks. Acetone can be produced from abundantly available biomass, such as agricultural wastes, by ABE (acetone-butanol-ethanol) fermentation [4]. During the first part of the 20th century the anaerobic production of ABE by solventogenic clostridia, aimed at the production of acetone for the war industry, was the second largest biotechnological process in the world. Although the petroleum-based production of solvents replaced this process, the shortage of fossil fuels in the near future has revived interest in the subject and much effort is now being devoted to improve ABE production from biomass [5]. The catalytic steam reforming of bioethanol also produces acetone and hydrogen by using catalysts such as CuO/CeO2 [6]. Acetone is also an important oxygenate component of the biomass pyrolysis oils, whose up-grading by reduction of their oxygen content is actively pursued [7,8]. Very recently, Tago et al. [9–11] have reported the chemical transformation of different biomass wastes, such as sewage sludge, fermentation residues and livestock manure, into acetone by using a ZrO2-FeOx catalyst. The transformation of acetone into hydrocarbons is a complex process which seems to takes place via acetone aldolization and dehydration followed by cyclization, aromatization and cracking, among other reactions [12,13]. Acetone has been converted into gasoline through a great variety of heterogeneous acid and basic catalysts [14] including several acid and basic zeolites [15,16]. Hutchings et al. [17] compared the catalytic activity of the proton forms of zeolites β and ZSM-5 in the transformation of acetone into hydrocarbons. They demonstrated that high isobutene selectivities can be achieved at high acetone conversion using zeolite β as catalyst, in contrast to the low selectivity attained with zeolite ZSM-5. Although they reported a selectivity to C6+ below 3% for an acetone conversion close to 65%, other authors in later studies found much higher conversion of acetone to aromatics (over 30% in some cases) [18,19]. Very recently, the conversion of acetone to hydrocarbons has also been investigated on alkaline and alkaline-earth exchanged beta zeolites [18,19]. The exchanged samples exhibited a higher selectivity to isobutene than the protonic zeolite, in particular those containing potassium and barium as metal cations. Many catalytic applications of zeolites involve the modification of their acid-base and redox properties by exchange with different metal cations [20]. Although extensively investigated for many zeolitic structures, metal cation-exchange on zeolite β has been studied less [21]. Herein we describe the ion exchange of zeolite β with different metal cations and their use as catalysts in the transformation of acetone into hydrocarbons. The materials have been characterized and the aliphatic and aromatic compositions of the products in the catalyzed reaction have been determined in order to evaluate the influence of the exchanged metals in the activity and selectivity of zeolite β. Materials 2012, 5 123 2. Results and Discussion 2.1. Characterization The XRD patterns of the metal exchanged zeolite β (Figure 1) were almost identical to that of the protonic zeolite [22]. No diffraction lines corresponding to oxide crystallites were observed, thus indicating that metal cations were well dispersed on the zeolite. However, there was a certain loss of crystallinity (Table 1), which was particularly significant for the Fe-β and Pb-β materials. Silicon to aluminium ratios slightly increased for most exchanged zeolites compared to that of the parent zeolite β (Table 1). Two of the new materials, however, underwent considerable dealumination, i.e., the 3+ 3+ chromium and the iron exchanged samples. The pKa values for Cr and Fe are 4.0 and 2.2 respectively, whereas they range between 9 and 11 for the remaining cations. Clearly, the Si/Al ratio increased with the acidic character of the exchanged cations. Even though the same exchange procedure was used for all samples, each metal cation was incorporated to zeolite β in a different extension. Cu2+ and Pb2+ were almost quantitatively exchanged giving rise to very high exchange degrees (98% and 84%, respectively). The lowest metal to aluminum ratios were obtained after exchange with Mn2+ and Ni2+, whereas Zn2+ and Co2+ also had a significant Me/Al ratio. The high content in Fe3+ (4.8% of the total sample weight) revealed the presence of such metal not only as an exchanged cation but also as oxide-like species consisting of very small (<3–4 nm) or disordered crystallites [23]. Figure 1. Powder X-ray diffraction patterns for metal exchanged β zeolites. Materials 2012, 5 124 Table 1. Some characteristics of metal exchanged β zeolites 1. Si/Al Metal content Me/Al Exchange Crystallinity Catalyst ratio (%) ratio degree (%) (%) H-β 12.5 - - - 100 Cr-β 27.9 1.00 0.44 - 94 Mn-β 15.3 0.89 0.23 46 83 Fe-β 49.9 4.80 3.77 - 64 Co-β 13.7 1.44 0.35 70 90 Ni-β 15.5 0.80 0.21 43 81 Cu-β 13.7 2.06 0.48 98 84 Zn-β 16.2 1.22 0.32 64 99 Al-β 14.5 - - - 86 Pb-β 16.7 1.50 0.42 84 65 1 See experimental section for details. Figure 2. Representative N2 adsorption-desorption isotherms for metal exchanged β zeolites. All zeolites exhibited a combined type I and IV isotherm adsorption behavior due to the presence of zeolitic micropores as well as mesopores formed by the aggregation of crystals (Figure 2). No new mesoporosity was generated after the ion exchange treatment. All samples experienced a non-negligible decrease in their surface area (Table 2). In general, both micropore and mesopore volumes were smaller for the exchanged zeolites than for sample H-β. However, this decrease in volume was more Materials 2012, 5 125 pronounced for the micropores (ca. 20% compared to 10% as much for mesopores) as a result of the preferential location of the exchanged cations inside the micropores of the zeolite. Table 2. Surface properties of metal exchanged β zeolites. 2 −1 3 −1 3 −1 Catalyst SBET (m g ) Mesopore volume (cm g ) Micropore volume (cm g ) H-β 582 0.89 0.22 Cr-β 540 0.88 0.19 Mn-β 531 0.90 0.19 Fe-β 513 0.89 0.18 Co-β 513 0.79 0.19 Ni-β 505 0.84 0.17 Cu-β 499 0.84 0.18 Zn-β 525 0.89 0.19 Al-β 522 0.85 0.19 Pb-β 545 0.85 0.18 Figure 3 depicts the population of acid sites determined by pyridine desorption. All materials adsorbed a significant amount of pyridine. Pyridine can be adsorbed in both Brönsted and Lewis acid sites [19]. Zeolites Cr-β and Fe-β showed the lowest pyridine adsorption due to their higher Si/Al ratios caused by their dealumination during ion-exchange. The zeolites with the greatest number of strong and medium acid sites were H-β and Al-β whereas metal exchanged zeolites showed higher populations of weak acid sites. Thus, those weak Lewis acid sites generated after ion exchange desorbed pyridine at lower temperatures. Zeolites exchanged with trivalent cations (Cr3+, Fe3+ and Al3+), however, did not exhibit such an increase in the population of weak acid sites whilst the Cu-β sample, which was almost quantitatively exchanged, had Lewis sites able to adsorb pyridine up to 350–550 °C.
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